Mechanisms of lipid peroxidation: iron catalyzed decomposition of fatty acid hydroperoxides as the basis of hydrocarbon evolution in vivo.

Ethane and pentane are evolved during peroxidation of tissue lipids in vivo and are believed to be derived from omega3 and omega6 fatty acids respectively. We present evidence supporting a scission mechanism as the means of forming these hydrocarbons during hydroperoxide decomposition. A fatty acid omega6 hydroperoxide (methyl 13-hydroperoxy-6,9,11-octatrienoate), when incubated with a ferrous ion, yielded pentane as the major hydrocarbon (98%). Reaction with ferrous ion results in an alkoxy capable of undergoing scission to an aldehydic fatty acid and a hydrocarbon.